FR2840915A1 - Production of architectural silicone membranes comprises coating an architectural textile with an aqueous emulsion of a polyaddition-crosslinkable polyorganosiloxane composition containing an adhesion promoter - Google Patents

Abstract

Production of architectural silicone membranes comprises coating an architectural textile with an aqueous emulsion of a polyaddition-crosslinkable polyorganosiloxane composition containing 0.005-10 wt.% of an adhesion promoter which is a protective hydrocolloid or a hydroxy- and ammonium-functional silane or POS, and crosslinking the product to give a coating/textile dry weight ratio below 0.2. Production of architectural silicone membranes comprises: (a) coating an architectural textile with an aqueous emulsion containing a polyorganosiloxane (POS) with at least two silicon-bonded C2-C6 alkenyl group, a POS with at least three silicon-bonded hydrogen atoms, 0.005-10 wt.% of an adhesion promoter which is a protective hydrocolloid or a hydroxy- and ammonium-functional silane or POS, a catalyst, a surfactant, optionally a POS resin with at least two alkenyl groups, a crosslinking inhibitor, optionally a pH-fixing agent, optionally one or more formulation aids and optionally a filler; and (b) crosslinking the product to give a coating/textile dry weight ratio below 0.2. An Independent claim is also included for a membrane produced as above.

Description

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Method for coating an architectural textile with at least one layer of silicone elastomer, from an aqueous silicone emulsion and architectural textile thus coated
The present invention relates to a method for coating an architectural textile with at least one layer of silicone elastomer, obtained from an aqueous polyorganosiloxane (POS) emulsion, applicable and crosslinkable in a thin layer on the support and to architectural silicone membranes thus obtained.

 More specifically, the invention relates to the production of architectural silicone membranes obtained from a silicone coating of an architectural textile, in particular but not limited to a glass fabric.

 This embodiment consists of depositing a liquid silicone composition on the architectural fabric and then ensuring that the applied thin layer crosslinks (hardens) and transforms into an elastomer.

 "Architectural textile" means a fabric or non-woven material and, more generally, any fibrous medium intended for use after covering the clothing industry: shelters, mobile structures, textile buildings, partitions, flexible doors, tarpaulins, tents , stands or marquees; furniture, cladding, advertising screens, windbreaks or filter panels; sun protection, ceilings and blinds.

 In particular, silicone coatings act as binder intended to improve the mechanical properties of architectural textiles, in particular the tear resistance, the fraying resistance, the flexibility or even the wrinkling ability.

 Silicone coatings can also help to give architectural textiles some impermeability and water repellency.

 In the case of noncombustible architectural textiles such as glass fabrics, it is important that these silicone coatings do not increase the resistance to combustion and especially the calorific value of such textiles.

 In addition to protecting textiles against heat and fire, silicone coatings can also provide protection against

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 other aggressions and / or give them specific properties for certain applications (dielectric properties for example).

 There are several important technical problems in producing elastomeric coatings on architectural textiles.

 A first problem is related to the deposition / impregnation operation of the non-crosslinked silicone composition on the textile. It is important that it can be done easily, quickly (industrial rate) and, for obvious economic reasons, with reduced deposition rates (for example less than 40 microns).

 A second problem lies in the minimum level of adhesion that the silicone coating must have on the textile.

 A third problem stems from the ambition to improve the performance of the silicone elastomer coating in terms of its mechanical properties, its protective function, and its water-repellent and waterproof properties, without affecting the non-combustibility qualities of the silicone elastomer coating. some architectural textiles such as glass fabrics.

 Taking into account the first problem referred to above led those skilled in the art to liquid silicone compositions of the type aqueous silicone emulsions with or without a load. It remains to be seen whether these emulsions make it possible to correctly satisfy the second and third problems mentioned above.

co-diméthylhydroxysiloxy, en émulsion dans l'eau en présence d'un émulsifiant anionique, - un promoteur d'adhérence (B). qui est choisi dans le groupe comprenant : le produit de réaction entre, d'une part, un silane amino-fonctionnel ou un hydrolysat de celui-ci, et d'autre part, un anhydride d'acide, un silane époxy-fonctionnel ou un hydrolysat de celui-ci et/ou un organosilane ayant un radical isocyanate et un radical hydrolysable ou un hydrolysat de celui-ci, (cf. exemple 3- amino-propyltriéthoxysilane +anhydride maléique), une silice colloïdale (C), et un catalyseur (D). European Patent Application EP-A-0 535 649 discloses a method of coating airbag air bags comprising a silicone emulsion comprising: a polyorganosiloxane (A) of the type POS: PDMS a,

co-dimethylhydroxysiloxy, emulsified in water in the presence of an anionic emulsifier, - an adhesion promoter (B). which is selected from the group consisting of: the reaction product between, on the one hand, an amino-functional silane or a hydrolyzate thereof, and, on the other hand, an acid anhydride, an epoxy-functional silane or a hydrolyzate thereof and / or an organosilane having an isocyanate radical and a hydrolyzable radical or hydrolyzate thereof (see Example 3-aminopropyltriethoxysilane + maleic anhydride), a colloidal silica (C), and a catalyst (D).

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 The emulsion used in this process suffers from the following drawbacks: insufficient compromise in terms of adhesion, reactivity and stability of the emulsions, in particular insufficient adhesion of the silicone to the support, incompatibility of the silanes and the surfactant used with the polyaddition systems based on #SiH oils and Platinum catalyst.

 Similarly, the European patent application EP-A-0 552 983 describes a coating method with an emulsion of the same type obtained from (A) an organopolysiloxane having at least two alkenyl [poly (dimethyl) (vinylmethyl) groups. ) siloxane alpha, omega-dimethylvinylsiloxy], (B) an organohydrogenpolysiloxane [poly- (methylhydrogeno) siloxane alpha, omega-trimethylsiloxy] having at least three hydrogen atoms and (C) a platinum crosslinking catalyst, (D) ) an ethynylcyclohexanol type crosslinking inhibitor, (E) an epoxidized trialkoxysilane or aminofunctional silane adhesion promoter (p.4, line 34), and (F) optionally a reinforcing filler such as a colloidal silica by emulsification in water in the presence of an emulsifier (dodecylbenzenesulfonate and polyvinyl alcohol APV).

The emulsion used in this coating process suffers from the following disadvantages: insufficient adhesion (on the substrate) / stability (of the emulsion), in particular the use of dodecylbenzene sulphonate and non-salified amino-functional silane, leads to a stability limited polyaddition emulsions.

siloxane a,w-triméthylsiloxy ; 3- un catalyseur au platine du type platine de Karstedt ; 4- un promoteur d'adhérence produit par la réaction entre un vinyle triacétoxysilane et un triméthoxysilane fonctionnalisé par un radical glycidyle ; 5- un inhibiteur de réticulation du type éthynylcyclohexanol ; 6- une résine silicone de type MT avec M = (Me3Sio1/2) et T = (MeSi03/2) ; 7- un émulsifiant du type dodécylbenzène sulfonate de sodium. European Patent EP-B-0 758 666 relates to the coating of flexible supports with an aqueous emulsion comprising:
1- polydimethylsiloxane-type POS (PDMS) end-vinylated (vinyldimethylsiloxy);
2- hydrogenated POS of poly (methylhydrogen) (dimethyl) type -

α, β-trimethylsiloxy siloxane; 3- a platinum catalyst of the Karstedt platinum type; An adhesion promoter produced by the reaction between a vinyl triacetoxysilane and a trimethoxysilane functionalized with a glycidyl radical; 5- a crosslinking inhibitor of the ethynylcyclohexanol type; 6- a type MT silicone resin with M = (Me3SiO1 / 2) and T = (MeSiO3 / 2); An emulsifier of the sodium dodecylbenzene sulphonate type.

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This silicone polyaddition emulsion finds a preferred application for the production of textile coating coatings ("airbag": polyamide support).

 European Patent Application EP-A-1 010 721 discloses the same emulsion as that described in EP-B-0 758 666, with an additional additive consisting of carbon black.

 Patent application FR-A-2 738 830 relates to the coating of textile material with an aqueous emulsion of polyorganosiloxanes. This emulsion is obtained by mixing a pre-emulsion A and a pre-emulsion B.

- 1- de l'huile POS de type PDMS a,co-diméthylvinylsiloxy ; - 2- d'une huile POS hydrogénée du type PDMS [alpha],#- diméthylhydrogénosiloxy ; - 3- une huile à silicone POS hydrogénée du type poly(diméthyl)(méthylhydrogéno)siloxane ; - 4- un promoteur d'adhérence du type vinyltriméthoxysilane, 3- glycidoxypropyltriméthoxysilane (GLYMO), 4-époxycyclohexyl- éthyltriméthoxysilane, chélates de type orthotitanate de butyle, ou enfin s'agissant des compositions silicones réticulables par polyaddition, des silanes aminés de type triméthoxy ou triéthoxysilane amino-fonctionnel) ; - 5- un inhibiteur de réticulation du type éthynylcyclohexanol ; - 6- et charges = silice colloïdale hydrophobée dans de l'huile silicone. Preemulsion A comprises:

PDMS α, α-dimethylvinylsiloxy POS oil; 2- a hydrogenated POS oil of the type PDMS [alpha], # -dimethylhydrogensiloxy; A hydrogenated POS silicone oil of the poly (dimethyl) (methylhydrogen) siloxane type; An adhesion promoter of the vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane (GLYMO), 4-epoxycyclohexylethyltrimethoxysilane, chelates of the butyl orthotitanate type, or finally, in the case of polyaddition crosslinkable silicone compositions, trimethoxy-type amino silanes; or amino-functional triethoxysilane); A crosslinking inhibitor of the ethynylcyclohexanol type; And 6- fillers = hydrophobicized colloidal silica in silicone oil.

Preemulsion B comprises: - 1 '- a co-divinylated POS a oil identical to that of the emulsion A; - 4'- an adhesion promoter of the butyl titanate type; A platinum catalyst; - 6'- of the colloidal charge of the same type as in emulsion A.

Preemulsions A and B are respectively prepared by stirring the above-described compositions in the presence of water and polyvinyl alcohol (APV 25/140 Rhodoviol). Once obtained separately, the preemulsions A and B are mixed with each other.

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The process for preparing this aqueous silicone emulsion is not optimized. The following drawbacks can be noted: very coarse emulsion, process which is not very flexible and expensive because it is necessary to produce intermediate silicone mixtures, difficulty of preparing very concentrated emulsions.

 In this state of the art, one of the essential objectives of the present invention is to provide a method for coating an architectural textile, using a silicone emulsion crosslinkable by polyaddition and provided with rheological properties such that it can be easily deposited / applied to the architectural fabric, at high speed, and with limited deposition rates, for example less than 40 g / m2.

 Another essential object of the invention is to provide a method for forming fine coatings (thin layers) for protecting architectural textiles, these silicone elastomer coatings having excellent mechanical properties (cohesion, flexibility), and conferring on the architectural textile a good resistance to fraying and tearing and good wrinkling ability.

 Another essential object of the invention is to provide a method for forming fine coatings (thin layers) for protection of architectural textiles, in which the deposition is easy, the amounts of emulsion used are limited and which leads to silicone-coated substrates with good incombustibility qualities expressed for example by a higher heating value measured according to NFP 92510 of less than 4200 kJ / kg and preferably less than 2500 kJ / kg.

 Another essential object of the invention is to provide a process for forming on inorganic or polymer architectural textiles which are not very suitable for adhesion, silicone coatings adhering to the fibers and conferring on them non-adherent, water-repellent, impermeable and protective properties. easy deposit and quantity specifications and reduced cost.

 Another essential object of the invention is to provide a silicone coating process on architectural textiles, to form protective elastomeric coatings, impermeable, optionally incombustible, flexible, resistant, using an emulsion composition such that for architectural textiles, the elastomeric film is a good binder capable of giving strength, cohesion and flexibility to coated textiles, while minimizing the phenomenon of crease marking.

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 Another essential objective of the invention is to provide a silicone coating process in which a stable, chemically (preservation of = SiH and reactivity) and physically (limited creaming and coalescence during storage of the emulsion) emulsion is implemented. emulsion), and having good characteristics in terms of reactivity (crosslinking by polyaddition) and adhesion to the support, by drying the treated textile.

 Another essential objective of the invention is to provide a method of coating an architectural textile, using an aqueous silicone emulsion crosslinkable by polyaddition and having the specifications set out above, this process must be simple economic, industrial, while allowing to produce architectural textiles coated, flexible, not subject to folding, resistant to tearing, fraying and possibly endowed with an incombustible character expressed for example by a higher calorific value (PCS) measured according to NFP 92510 less than 4200 kJ / kg and preferably less than 2500 kJ / kg.

 Another essential object of the invention is to provide architectural textiles coated with a silicone elastomer thin film resulting from the coating and the crosslinking by polyaddition of an aqueous silicone emulsion, according to a process of the type defined in the objectives above, these coated architectural textiles being intended for the production of membranes for indoor and outdoor textile architecture and sun protection.

 These objectives, among others, are achieved by the present invention, which firstly concerns a method for producing architectural silicone membranes by coating an architectural textile with at least one layer of silicone elastomer, characterized in that it comprises the following steps: # a deposition step on said architectural textile; at least one layer of an aqueous polyorganosiloxane (POS) elastomeric crosslinkable emulsion by polyaddition reactions and comprising: (A) at least one POS having per molecule at least two C2-C6 alkenyl unsaturated functional groups; , bonded to silicon, (B) at least one POS having per molecule at least three silicon-bonded hydrogen atoms

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 (C) at least one special adhesion promoter chosen from the group of compounds comprising protective hydrocolloids, silanes and / or hydroxylated POSs carrying, per molecule, at least one hydroxyl group and at least one amino and salified function and mixtures thereof, with the proviso that the weight percentage of the adhesion promoter (C) relative to the silicone phase is strictly in the range of 0.005 to 10%, preferably 0.03 to 5%. and more preferably still from 0.05 to 4%, (D) at least one catalyst, (E) at least one surfactant, (F) optionally at least one POS resin comprising at least two alkenyl groups, (G) at least a crosslinking inhibitor, (H) optionally at least one pH-fixing agent, (I) optionally at least one formulation additive, (J) optionally a filler, (K) and water, # then a step of crosslinking, so as to obtain an architectural textile it is coated with an elastomer layer, so that the ratio of the weight of the coating expressed in dry matter to the weight of the architectural fabric is less than 0.2 and preferably between 0.05 and 0.11.

Preferably, the weight ratio of adhesion promoter (C) / surface developed by the textile is in the range of 0.1 to
10 mg / m 2, preferably 0.2 to 5 mg / m 2.

 By "surface developed by the textile" is meant in accordance with the invention the surface developed by the fibers constituting the architectural fabric and which will be covered by the emulsion.

 The depositing step is advantageously a coating.

 The coating step can in particular be carried out by squeegee, in particular by squeegee on a cylinder, squeegee in the air and scrape on carpet, by padding, in particular by squeezing between two rollers or else by a nap roller, rotary frame, inverse roller "reverse roll", by transfer, by screen printing, by heliography, or by spraying.

 It is possible to coat one or both sides of the textile material, the coating of the two faces then being advantageously carried out by

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 padding after impregnation of the fabric with the emulsion. After passing between the rollers, the textile is uniformly coated with a thin layer of emulsion. The drying and crosslinking are then carried out, preferably by hot air or infra-red, especially from 30 seconds to 5 minutes, at a crosslinking temperature without exceeding the degradation temperature of the substrate.

 When the coating is carried out on one side, a doctor blade is preferably used. The emulsion is deposited continuously on the upper face of the textile, then passes under the doctor blade, before drying and crosslinking as above.

 Preferably, the coating is carried out: by immersion of the architectural fabric in an emulsion bath as defined above, # by dewatering, preferably by pressure between rollers, # then by crosslinking, preferably under thermal activation when the crosslinking is carried out according to a polyaddition mechanism.

 The elastomer layer is preferably between 5 and 200 g / m 2. In the case of a two-component emulsion, the process comprises a preliminary step consisting in mixing the two components.

 Advantageously, the architectural fabric is a fabric, a nonwoven, a knit or more generally any fibrous support comprising fibers and / or fibers selected from the group of materials comprising: glass, silica, metals, ceramics, silicon carbide, carbon, boron, natural fibers such as cotton, wool, hemp, flax, artificial fibers such as viscose, or cellulosic fibers, synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofibres, polyolefins, synthetic rubbers, polyvinyl alcohol, aramids, fluorofibres, phenolics ...

 Remarkably, the architectural fabric when it is chosen from inorganic materials such as glass, silica, metals, ceramics, silicon carbide, carbon, boron, has, once coated, a calorific value. Higher (PCS) which is less than or equal to 4200 kJ / kg, preferably less than or equal to 2500 kJ / kg.

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 Advantageously, the coated architectural textiles have a total weight of less than 1200 g / m 2 and preferably between 100 and 500 g / m 2 and make it possible to produce composite membranes having good non-combustibility properties for the interior and exterior architecture or the sunscreen .

 The aqueous silicone emulsion used in the process according to the invention is of the type that can be crosslinked by polyaddition at room temperature (EVF or RTV), knowing that this platinum catalyzed crosslinking can be thermally activated (100-200 ° C.). .

 The aqueous silicone emulsion of the process according to the invention is adhered to numerous architectural textiles, for example glass fibers, possibly synthetic textile fibers, of the polyester or polyamide type.

 With regard to architectural textiles of the inorganic type, the process using the emulsion supra makes it possible to obtain glass fabrics coated with silicone elastomers in thin, water-repellent layers having good mechanical properties of flexibility, resistance to tearing and tearing. fraying and with a low heating value (eg PCS <2500 KJ).

 One of the essential constituents of the emulsion used in the process according to the invention is the special adhesion promoter (C), judiciously selected so that the adhesion is provided: by at least one protective hydrocolloid, preferably VPA, which may also act as surfactant (E) in combination or not with other emulsifiers, or by silanes and / or specific, judiciously selected POSs, namely silanes and / or Hydroxylated and amino-salified POSs, or else by a protective hydrocolloid, preferably APV, and silanes and / or hydroxylated and amino-salified POSs.

 According to a first embodiment of the invention, the protective hydrocolloid, preferably APV, is exclusively dedicated to the adhesion promoter function (C).

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 According to a second embodiment of the invention, the surfactant (E) may be at least partly constituted by at least one protective hydrocolloid, preferably an APV.

 In the first embodiment, the protective hydrocolloid, preferably PVA, is present in a reduced amount in the emulsion so that it can only fully exercise its adhesion promoter function (C) and imperfectly its emulsifying function. As a result, the emulsion must comprise a primary emulsifier or surfactant (E).

In the second embodiment of the invention, the protective hydrocolloid, preferably the APV, adhesion promoter and emulsifier, is present in a proportion of 1.5 to 7% of dry APV relative to the total mass of silicone oils.

 From a qualitative standpoint, it can be indicated that the protective hydrocolloid is preferably a polyvinyl alcohol (PVA) or a mixture of PVA and, preferably, PVA grades which in aqueous solution (at 4% and at 20 C) have a typical dynamic viscosity (#dt) of between 5 and 40 mPa.s, preferably between 10 and 30 mPa.s, and an ester number of greater than or equal to 80, preferably 100, and especially between 120 and 200; .

 Preferably, the PVA is used in the form of an aqueous solution of dynamic viscosity type (#dt) of between 5 and 40 mPa.s, preferably between 10 and 30 mPa.s, and whose ester number is greater than or equal to 80, preferably 100 and in particular between 120 and 200.

 Polyvinyl alcohols (PVA) are compounds obtained indirectly from their esters, by hydrolysis in an aqueous medium or by alcoholysis in an anhydrous medium. In practice, the esters used as raw material are commonly polyvinyl acetates. Generally, the lysis of the esters leading to APV is not complete. It remains in the molecule acyl radicals whose proportion affects the properties of the PVA, including its solubility. A mode of definition of VPAs is therefore based on the indication of the ester number (I.E) which is inversely proportional to the degree of hydrolysis. The measure of I.E. is carried out in a manner known per se, by neutralization of the possible acidity of the polyvinyl alcohol, saponification of the acyl groups and titration of the excess of alkalinity.

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 The polyvinyl alcohols according to the invention are also characterized by the degree of condensation which can be evaluated by the determination of the dynamic viscosity of a standard solution (denoted by #dt in the present disclosure), given that this variable is as much as the degree of condensation is greater.

 The viscosity #dt corresponds to the dynamic viscosity coefficient of an aqueous solution of APV at 4% by weight, measured at a temperature of 20 ° C. using an Ostwald viscometer.

 As another protective hydrocolloid, mention may also be made of hydrosdispersible sulphonated polyesters, especially of the sulfonated polyethylene terephthalate type.

 The water-dispersible sulfonated polyesters are known and commercially available products. They can be prepared by co-condensation of an organic diacid (such as a saturated or unsaturated aliphatic diacid, an aromatic diacid, a diacid having a plurality of aromatic nuclei, an arylaliphatic diacid), one of diesters or its anhydride and of a sulfonated organic diacid or one of its diesters with a diol, in the presence of a usual polyesterification catalyst such as tetraisopropyl orthotitanate.

 As starting monomers commonly used for the preparation of sulphonated, water-dispersible polyesters, mention may be made, as: organic diacids: saturated or unsaturated aliphatic diacids, aromatic diacids, such as succinic, adipic, suberic, sebacic acids, maleic, fumaric, itaconic acids, orthophthalic, isophthalic, terephthalic acids, anhydrides of these acids and their diesters such as methyl, ethyl, propyl, and butyl diesters. The preferred compounds are adipic acid, orthophthalic, isophthalic and terephthalic acids; - Sulfonated organic diacids: sodium diacid sulfonates or their diesters such as dialkylisophthalates and dialkylsulfosuccinates such as sodium 5-dimethylisophthalate sulfonate or sodium dimethylsulfosuccinate; diols: aliphatic glycols such as ethylene glycol, diethylene glycol, dipropylene glycol and higher homologues, 1,4-butanediol, 1,6-hexane diol, neopentyl glycol and cyclanic glycols such as cyclohexanediol, dicyclohexane diolpropane.

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 The diols chosen preferentially are ethylene glycol and diethylene glycol.

 The preferred water-dispersible sulfonated polyesters are those which have a number-average molecular weight of between 10,000 and 35,000, an acid number of less than 5 mg KOH / g, a sulfur content of between 0.8 and 2. % by weight, preferably between 1.2 and 1.8%. As polyesters of this type, it is possible in particular to use the products marketed by Rhodia under the trademark GEROL PS20.

 The hydroxylated and aminosalified silanes which may be constitutive elements of the promoter (C) are obtained from non-salified precursors, among which there may be mentioned as examples monoaminetrihydroxymonosilanes, such as: NH 2 (CH 2) 3 -Si (OH ) 3, possibly oligomerized by partial condensation of SiOH.

 That being said, the water-soluble adhesion promoter (C) preferably comprises hydroxylated, amino and salified POSs.

(Rl)xCR2)y(OH)z Si 04 ~ (x + y + z)
2 (I) dans laquelle : # R' représente un groupement monovalent exempt d'azote, de nature identique ou différente d'une unité récurrente à l'autre, et correspondant à un alkyle en C1-C6, un aryle, un alcényle en C2-C8, ou un acrylate, chacun de ces groupements étant éventuellement substitué, # Prêtant de nature identique ou différente d'une unité récurrente à l'autre et répondant à la formule suivante : - R4 - NI+) R5R6,X(-) * R4 étant un radical hydrocarboné en C1-C10, éventuellement substitué, * les groupements R5, R6sont identiques ou différents et représentent l'hydrogène ou un radical hydrocarboné en C1-C10, éventuellement substitué, ou -R4-NH3(+),X(-), These aminated and salified POS constituting the promoter (C) are the amino and salified POS constituting the promoter (C) are advantageously formed of several recurring units of average formula (I) following:

(R1) xCR2) y (OH) z Si O4 (x + y + z)
2 (I) wherein: # R 'represents a monovalent group free of nitrogen, of the same or different nature from one recurring unit to another, and corresponding to a C 1 -C 6 alkyl, an aryl, an alkenyl, C2-C8, or an acrylate, each of these groups being optionally substituted, # Lending identical in nature or different from one recurring unit to another and having the following formula: - R4 - NI +) R5R6, X (-) R4 being a C1-C10 hydrocarbon radical, optionally substituted, the groups R5, R6 are identical or different and represent hydrogen or an optionally substituted C1-C10 hydrocarbon radical, or -R4-NH3 (+), X (-)

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 or else the groups R 5 and R 6 are different from hydrogen and together form a 5-7 membered ring containing at least one heteroatom, preferably nitrogen or oxygen, and X representing a chosen counteranion among carboxylates, halides and; # x, y and z are positive integers or decimals less than 4; # and x + y + z <4.

 Preferably, the aminated and salified POS is a resin having an average silicon functionality greater than 2, corresponding to x + y <2: # x being preferably <2 and more preferably still 0.1 # x # 1; # y being preferably <1.2 and more preferably still 0.1 x 1.1.

This corresponds to a POS resin: # on the one hand, hydroxylated and comprising siloxyl units T and optionally M and / or D and / or Q or even siloxyl units Q and M and / or D and / or T; # on the other hand, bearing at least one amino and salified pattern.

 The siloxyl units M, D, T, Q of the POS (C) are defined as follows: - M = R3 SiO1 / 2 - unit D = R2 Si02 / 2 - T = RSiO3 / 2 - Q = SiO4 / 2 The radicals R are identical or different and correspond to: o a radical R1 as defined above (for example an alkyl radical (eg methyl, ethyl, isopropyl, tert-butyl and n-hexyl), a hydroxyl, alkenyl (eg vinyl , allyl) o or else an aminosalifiable or salified R2 moiety as defined above.

By way of example of linear hydroxylated POS resin, usable as a promoter (C), mention may be made of poly (methyl siloxane), both ends of which comprise a hydroxyl and of which each silicon atom carries an aminosalifiable or salified unit.

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The resins more particularly selected are those of the type T (OH), DT (OH), DQ (OH), DT (OH), MQ (OH), MDT (OH) MDQ (OH) or mixtures thereof. In these resins, each OH group is carried by a silicon atom belonging to a D, T or Q unit.

These resins are condensation products (mono or hetero condensation polycondensation or homo condensation) of monomers, oligomers or POS polymers bearing condensable groups, preferably of hydroxylic nature.

In addition to these hydroxyls, the promoter (C) comprises one or more aminosalifiable or salified units identical to or different from each other.

In these units, the amine may be primary, secondary or tertiary. According to variants, it can be included in a cycle or be included in isocyanurate groups or HALS (piperidine type or other).

dans laquelle : # les radicaux R, identiques ou différents entre eux, sont choisis parmi les radicaux alkyles, linéaires ou ramifiés, ayant de 1 à 3 atomes de carbone, phényle et benzyle ; # R8 est choisi parmi un atome d'hydrogène, les radicaux alkyles linéaires ou ramifiés, ayant de 1 à 12 atomes de carbone, les radicaux allkylcarbonyles, où le reste alkyle est un reste linéaire ou ramifié ayant de 1 à 18 atomes de carbone, les radicaux phényle et benzyle et un radical 0 ; # t est un nombre choisi parmi 0 et 1 ; # de préférence les radicaux R7 sont des méthyles, le radical R8 est un nombre d'hydrogène ou un radical méthyle et t étant avantageusement un nombre égal à 1 . Within the meaning of the invention, the HALS groups can be defined as a cyclic hydrocarbon chain (HALS) of formula:

in which: the radicals R, which are identical to or different from one another, are chosen from linear or branched alkyl radicals having from 1 to 3 carbon atoms, phenyl and benzyl; # R8 is chosen from a hydrogen atom, the linear or branched alkyl radicals having from 1 to 12 carbon atoms, the alkylcarbonyl radicals, where the alkyl radical is a linear or branched radical having from 1 to 18 carbon atoms, phenyl and benzyl radicals and a radical O; # t is a number selected from 0 and 1; the radicals R7 are preferably methyl, the radical R8 is a hydrogen number or a methyl radical and t is advantageously a number equal to 1.

The aminosalifiable or salified units are advantageously chosen so that they are able to bind with the textile support on which the emulsion

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 is applied, so as to provide adhesion, without jeopardizing the desirable water solubility for the promoter (C).

For more details on these promoters (C) of the water-soluble, aminosalifiable or salified and hydroxylated silicone resin type, and on obtaining them, reference will be made to patent FR-B-2,753,708 or to the European patent application EP-A- 0 675 128.

de manière optionnelle, le promoteur comportant des motifs aminosalifiables peut aussi porter des fonctions non aminées, telles que les suivantes : - 3-méthacryloxypropyl : (H2C = C)(CH3) (COO)(CH2)3-

/ "" - 3-glycidyloxypropyl : H2C -CH -CH20(CH273- - 3-mercaptopropyl : (HS) (CH2)-3 - 3-chloropropyle : (CI)(CH2)-3 As specific examples of aminosalifiable units, there may be mentioned in particular: aminopropyl: (H 2 N) (CH 2) -3-N-methyl-3-aminopropyl: (H 3 CNH) (CH 2) 3 -N-aminoethyl-3 aminopropyl: (H2N) (CH2) 2NH (CH2) -3-C6H5CH2NH (CH2) 2 (NH) (CH2) -3 -3-ureidopropyl: (H2NCO NH) (CH2) -3- 3-4.5- dihydroimidazol-1-yl-propyl:

optionally, the promoter comprising aminosalifiable units may also carry non-amino functional groups, such as the following: 3-methacryloxypropyl: (H 2 C = C) (CH 3) (COO) (CH 2) 3

3H-glycidyloxypropyl: H 2 CH 2 -CH 2 O (CH 2 O 3 - 3-mercaptopropyl: (HS) (CH 2) 3 - 3-chloropropyl: (Cl) (CH 2) -3

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 These units may be incorporated by techniques known to those skilled in the art, in particular by co-hydrolysis / co-condensation of an alkoxysilane amine with a non-amino alkoxysilane bearing the units described above.

It is also possible to add the alkoxysilanes carrying these non-amino units in the emulsion containing the saline amino silane.

 One of the essential characteristics of the promoter (C) selected according to the invention is to be salified through the amino units which are as described above and which comprise at least one of = N +, X -, with X representing a counteranion selected from carboxylates, halides, preferably a lactate, an acetate or a chloride.

For the promoter (C) to be salified, it is necessary to ensure that the aqueous continuous phase of the dispersion has a pH such that this promoter (C) (preferably a hydroxylated POS resin) is maintained in ionized form. The choice of pH is carried out, in a manner known per se, according to the pKa of the acid which corresponds to the counter-anion used.

The preferred promoter (C) in hydroxylated resin form is included in the aqueous continuous phase of the dispersion. It is solubilized or finely dispersed.

According to one variant, it is conceivable that only part of the promoter (C) is in salified form, the rest being unsalified.

Promoter mixtures (C) of different types are also covered by the invention.

 The silicone phase of the emulsion used in the process according to the invention comprises POSs for generating the elastomer by crosslinking / curing at room temperature (23 ° C.) according to a polyaddition mechanism. It is possible to accelerate the crosslinking by thermal activation at a temperature above ambient. The so-called cold vulcanizable polyaddition elastomers and the hot vulcanizable polyaddition elastomers are within the scope of the invention.

 These polyorganosiloxanes, main constituents of the compositions according to the invention, may be linear, branched or crosslinked, and may comprise hydrocarbon radicals and / or reactive groups such as, for example, hydroxyl groups, hydrolysable groups,

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 alkenyl groups, hydrogen atoms, etc. It should be noted that the organopolysiloxane compositions are amply described in the literature and in particular in the work of Walter Noll "Chemistry and Technology of Silicones", Academic Press, 1968,2th edition, pages 386 to 409.

et/ou de motifs siloxyles de formule :

More specifically, the POS, main constituents of the compositions according to the invention, consist of siloxyl units of general formula:

and / or siloxyl units of formula:

In these formulas, the various symbols have the following meaning: the R9 symbols, which are identical or different, each represent a nonhydrolyzable hydrocarbon-based group, this radical possibly being: an alkyl, haloalkyl radical having from 1 to 5 carbon atoms and comprising 1 to 6 chlorine and / or fluorine atoms, cycloalkyl and halogenocycloalkyl radicals having 3 to 8 carbon atoms and containing 1 to 4 chlorine and / or fluorine atoms, aryl, alkylaryl and halogenoaryls having from 6 to 8 carbon atoms and containing 1 to 4 chlorine and / or fluorine atoms; cyanoalkyl radicals having 3 to 4 carbon atoms; the symbols Z, identical or different, each represent a hydrogen atom, an alkenyl group; n = an integer equal to 0.1, 2 or 3; - - x = an integer equal to 0, 1, 2 or 3; y = an integer equal to 0.1 or 2; the sum x + y is between 1 and 3.

 By way of illustration, mention may be made of the organic radicals R 9 directly linked to the silicon atoms: the methyl groups; ethyl; propyl;

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dichlorométhyle ; a-chloroéthyle, a,p-dichloroéthyle ; fluorométhyle ; difluorométhyle [alpha],ss-difluoroéthyle ; trifluoro-3,3,3 propyle trifluoro cyclopropyle ; trifluoro-4,4,4 butyle ; hexafluoro-3,3,4,4,5,5 pentyle ; p- cyanoéthyle ; ss-cyanopropyle ; phényle ; p-chlorophénylem- ; chlorophényle ; dichloro-3,5 phényle ; trichlorophényletétrachlorophényle o-, p-, ou m-tolyle ; a-a-a-trifluorotolyle ; xylyles comme radicaux-2,3 phényle,radicaux-3,4 phényle. isopropyl; butyl; isobutyl; n-pentyl; t-butyl chloromethyl;

dichloromethyl; α-chloroethyl, α, β-dichloroethyl; fluoromethyl; difluoromethyl [alpha], ss-difluoroethyl; 3,3,3-trifluoropropyl trifluoro cyclopropyl; 4,4,4-trifluorobutyl; hexafluoro-3,3,4,4,5,5 pentyl; p-cyanoethyl; ss-cyanopropyl; phenyl; p-chlorophenylem-; chlorophenyl; 3,5-dichlorophenyl; o-, p-, or m-tolyl trichlorophenyletetrachlorophenyl; aaa-trifluorotolyl; xylyls as 2,3-phenyl radicals, 3,4-phenyl radicals.

 Preferably, the organic radicals R 9 bonded to the silicon atoms are methyl or phenyl radicals, these radicals possibly being optionally halogenated or else cyanoalkyl radicals.

 The symbols Z may be hydrogen atoms or vinyl groups.

 It is possible to use a wide variety of two-component or one-component organopolysiloxane compositions crosslinking at room temperature or with heat by polyaddition reactions, essentially by reaction of hydrogenosilyl groups with alkenylsilyl groups, in the generally presence of a metal catalyst, platinum, are described, for example, in US Pat. Nos. 3,220,972, 3,284,406, 3,336, 366, 3,697,473 and 4,340,709.

The organopolysiloxanes used in these compositions generally consist of pairs based on the one hand of at least one linear, branched or crosslinked polysiloxane consisting of units (III) in which the radical Z represents an alkenyl group and where x is at less than 1, optionally associated with units (II), and on the other hand at least one linear, branched or crosslinked hydrogen polysiloxane consisting of units (III) in which the radical Z then represents a hydrogen atom and where x is at least 1, optionally associated with units (II). As regards the unsaturated polysiloxane component (III), it may be an oil with a dynamic viscosity at 25 C of between 200 and 500,000 mPa.s. A mixture based on the abovementioned oil can be used as an ingredient, if necessary, with an unsaturated gum having a viscosity of greater than 500,000 mPa.s, which can be up to 106 mPa.s.

 Preferably, the emulsions used in the context of the invention also comprise, in the case of polyaddition compositions, at least one non-hydroxylated silicone resin (F). These silicone resins are well known and commercially available branched POS polymers. They

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 present, per molecule, at least two different units chosen from those of formula R103SiO1 / 2 (unit M), R102Si02 / 2 (unit D), R10SiO3 / 2 (unit T) and SiO4 / 2 (unit Q).

 The radicals R are identical or different and are chosen from linear or branched alkyl radicals, vinyl, phenyl and 3,3,3-trifluoropropyl radicals. Preferably, the alkyl radicals have from 1 to 6 carbon atoms inclusive. More particularly, there may be mentioned as R alkyl radicals, the methyl, ethyl, isopropyl, tert-butyl and hexyl radicals.

 Advantageously, in the polyaddition type emulsions, at least a portion of the radicals R10 are vinyl residues (weight content of Vi in particular between 0.1 and 2%). These vinyl functional groups are borne by the units M, D or T. As an example, mention may be made of vinylated MDQ resins, such as MDV @ Q, or else MMV @ Q resins.

 With regard to the surfactants (E) other than the protective hydrocolloid (APV), they may be anionic (except in the case where the emulsion comprises a saline amine as promoter (C)), cationic or nonionic, in particular may be one or more polyethoxylated fatty alcohols. Preferably, the surfactants (E) are nonionic. The role of the surfactant will notably be to refine the particle size of the emulsion and possibly to improve its stability.

 This emulsion may also comprise other formulation additives (1) such as: a condensation catalyst making it possible to promote the condensation of the silanols of silane or SAL-containing amine but not inhibiting platinum catalysis (for example titanium salts) , zirconium, or optionally certain tin salts), a bactericide, one or more inorganic or organic pigments, one or more organic thickeners (polyethylene oxide, xanthan gum, hydroxyethylcellulose, acrylic or cationic polymers, etc.) or minerals (laponite).

 Advantageously, the emulsion according to the invention comprises a system for maintaining the pH at alkaline values, for example between 7 and 8.

This system for maintaining the pH can be e. g. baking soda.

The pH setting and maintenance agent is preferably a buffer system comprising HCO3- / CO32- and / or H2PO4- / HPO42-. Thus, to obtain the desired buffering effect, it will be necessary to introduce according to the invention

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 a salt of HCO 3 - and / or H 2 PO 4 - such as, for example, NaHCO 3 and / or Na 2 CO 3 and / or NaH 2 PO 4 and / or Na 2 HPO 4. It goes without saying that any other salt with a different counter-anion (e.g., K) could be suitable. Particularly preferably, a buffer system consisting of NaHCO 3 which is incorporated in the emulsion is used in practice.

This allows the stabilization of the emulsion or coating bath or padding made by mixing emulsions. This provision is described in more detail in the patent application FR-A-2 773 166.

 Optionally, the emulsion may contain reinforcing or stuffing mineral fillers, which are preferably chosen from combustion silicas and precipitated silicas. They have a specific surface area, measured according to the BET methods, of at least 50 m 2 / g, especially between 50 and 400 m 2 / g, preferably greater than 70 m 2 / g, a mean average particle size of less than 0, 1 micrometer (m) and an apparent density of less than 200 g / liter.

 These hydrophilic silicas are preferably incorporated as such into the (continuous) aqueous phase of the emulsion. According to one variant, these silicas may optionally be treated with one or more organosilicon compounds usually used for this purpose. According to another variant, the silicas may be predispersed in the silicone oil. Among these compounds, there are methylpolysiloxanes such as hexamethyldisiloxane, octamethylcyclotetrasiloxane, methylpolysilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, chlorosilanes such as dimethyl-dichlorosilane, trimethylchlorosilane, methylvinyldichlorosilane, dimethylvinylchlorosilane, alkoxysilanes such as dimethyl-dimethoxysilane, dimethylvinylethoxysilane, trimethylmethoxysilane. During this treatment, the silicas can increase their starting weight up to a rate of 20%.

 It is also possible to use in addition to or instead of siliceous fillers other mineral fillers such as calcium carbonates, crushed quartz, calcined clays and diatomaceous earth, optionally in the form of aqueous dispersion ("slurry").

 In the case of non-siliceous mineral materials, they can be used as semi-reinforcing mineral filler, stuffing or with specific properties. Examples of these non-siliceous fillers that can be used alone or as a mixture are carbon black, titanium dioxide, oxide

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 aluminum, hydrated alumina, expanded vermiculite, unexpanded vermiculite, calcium carbonate, zinc oxide, mica, talc, iron oxide, barium sulfate and slaked lime. These fillers have a particle size generally of between 0.001 and 300 μm and a BET surface area of less than 100 m² / g.

 It is generally possible to use from 0.5 to 60% by weight, preferably from 10 to 25% by weight of filler, relative to the weight of the silicone phase of the formula.

The composition of the emulsion used in the context of the invention is, for example as follows: # 100 parts by weight of a co-divinylated POS (A) oil whose content of vinyl groups is included between 2 and 100 meq / 100g; # 0 to 150 parts by weight of a reinforcing, semi-reinforcing and / or stuffing charge dispersion (J) in water, or in an oil
POS a, co-divinylated (at the rate of 10 to 60% of charge in the dispersion); # 1 to 7 parts by weight of at least one oil POS (B1) to SiH, such that the ratio number of Si-H groups / number of Si-alkenyl groups ranges from 0.4 to 10, preferably from 0, 6 to 5; # 0.2 to 5 parts by weight of adhesion promoter (C), taken in the dry state; # a polyaddition catalyst (D), which is composed of at least one metal belonging to the platinum group, in a proportion of 2 to 150 ppm of platinum; # 0.5 to 10 parts by weight of surfactant (E); # 0 to 100 parts by weight of a POS resin (F); # 0 to 1 parts by weight of a crosslinking inhibitor (G); # 0 to n parts by weight of pH fixing agent (H), n being such that the pH is maintained between 7 and 8; # 0 to m parts by weight of a formulation additive (I); # 0 to 150 parts by weight of a reinforcing, semi-reinforcing and / or filling charge dispersion (J) in a POS [alpha], # -divinylated oil, at a level of 10 to 80% of filler in the dispersion ; # 40 to 2000 parts by weight of water (K), so that the final emulsion or bath (made by mixing several

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 emulsions and water), used for the treatment of the fabric, has a solids content of between 5 and 65%.

 According to another of its aspects, the present invention also relates to a process for preparing an aqueous POS emulsion as defined above, characterized in that an emulsification is carried out by introducing into the same reactor the constituents ( A) to (K).

 But preferably, the emulsion is produced by mixing pre-emulsions which are each unable to crosslink separately because they do not have all the reactive species and the necessary catalyst (POS = SiVi + POS = SiH + platinum) for polyaddition. For example, an emulsion containing the = SiVi and the #SiH and the inhibitor (part A), and a catalytic emulsion based on platinum and oil = SiVi (part B) can be produced, which will be associated during the confection coating bath.

 This greatly facilitates the production of a stable emulsion which can be easily prepared under industrial conditions. It is conceivable to use ingredients (A) and / or (B) and / or (C) in the form of pre-emulsions which may or may not contain the other ingredients (D) to (J).

 Thus, according to a variant: # the following pre-emulsions are carried out: (i) a pre-emulsion as base of POS (A), (ii) a pre-emulsion as base of POS (B) (cross-linking emulsion), ( iii) a pre-emulsion as base of the catalyst (D) (catalytic emulsion) consisting for example of an aqueous emulsion of a platinum catalyst diluted in a vinylated silicone oil; these pre-emulsions are mixed, one or the other of the pre-emulsions (i) to (iii) being able to contain, in addition, the surfactant (E), optionally the POS (F) resin, optionally the inhibitor crosslinking (G) and / or optionally the agent (H) for fixing the pH and / or optionally the formulation additive (1).

 Preferably the catalytic emulsion is added to the other silicone emulsions (in particular that based on SiH) during the formulation of the bath, before application to the architectural fabric.

 According to advantageous terms of the invention:

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 when the surfactant (E) is used as sole emulsifier, the emulsification is carried out directly or by phase inversion; # when using (in whole or in part) an APV (C) as sole emulsifier, emulsification is by direct route only; the direct route of casting the silicone phase in the aqueous solution containing the surfactant.

 Another advantageous embodiment of the invention may consist in the introduction of the adhesion promoter (C), in particular the silane or salified amino POS, only during the preparation of the coating bath.

 Another possibility could be to prepare parts A and B of emulsion or pre-emulsions (i), (ii), (iii) not containing adhesion promoter, to provide for the separate incorporation of the latter during mixture of A and B or (i), (ii), (iii).

 The present invention also relates to the aqueous emulsion of POS as defined above.

 The present invention also aims at any architectural silicone membrane that can be obtained according to the process according to the invention from an architectural textile: by depositing on the latter at least one layer of an aqueous polyorganosiloxane (POS) emulsion. crosslinkable elastomer by polyaddition reactions, and adapted to the impregnation of architectural textiles, and comprising: (A) at least one POS having per molecule at least two silicon-bonded C2-C6 alkenyl unsaturated functional groups, (B) at least one POS having, per molecule, at least three silicon-bonded hydrogen atoms (C) at least one special adhesion promoter selected from the group of compounds including protective hydrocolloids, silanes and / or hydroxylated POSs carriers per molecule of at least one hydroxyl group and at least one amino and salified function, and mixtures thereof, with the condition that the percentage by weight of the adhesion promoter (C) relative to the silicone phase is strictly in the range of 0.005 to 10%, preferably 0.03 to 5% and more preferably still 0.05 to 4 %

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 (D) at least one catalyst, (E) at least one surfactant, (F) optionally at least one POS resin comprising at least two alkenyl groups, (G) optionally at least one crosslinking inhibitor, (H) optionally at least one pH fixing agent, (I) optionally at least one formulation additive, (J) optionally a filler, (K) and water, - + then by crosslinking the POS contained in the emulsion deposited on the textile architectural.

 According to an advantageous arrangement of the invention, the architectural fabric is a fabric chosen from the group of materials comprising fibers and / or yarns chosen from the group of materials comprising: glass, silica, metals, ceramics, silicon carbide, carbon, boron, natural fibers such as cotton, wool, hemp, flax, artificial fibers such as viscose, or cellulosic fibers, synthetic fibers such as polyesters, polyamides, polyacrylics , chlorofibers, polyolefins, synthetic rubbers, polyvinyl alcohol, aramids, fluorofibers, phenolics.

 Remarkably, its Higher Heating Value (SCP) is less than or equal to 4200 kJ / kg and preferably less than or equal to 2500 kJ / kg.

 Advantageously, the architectural silicone membrane corresponding to a coated architectural textile as defined above or obtained by the process described above constitutes a membrane for the interior and exterior architecture or the sun protection.

 Such a membrane preferably has a weight of less than 1200 g / m 2 and preferably between 100 and 500 g / m 2.

 In addition to these flexible material membranes intended to be used in indoor or outdoor textile architecture (tarpaulins, tents, stands, marquees ...) or sun protection.

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 The thin-layer coated glass fabrics resulting from the coating and the crosslinking of the emulsion according to the invention are particularly interesting, in particular because of their good resistance to tearing and fraying. They are also flexible and are not subject to folding marking. In addition, their higher calorific value is low: PCS 4200 kJ / kg, and preferably # 2500 kJ / kg.

 The invention will now be described in more detail using non-limiting exemplary embodiments.

EXAMPLES
Example 1 Manufacture of Emulsions Used in the Process According to the Invention
1. 1 - Compounds used: - POS A-1: PDMS [alpha], # -dimethylvinylsiloxy oil, of dynamic viscosity (#dt) = 60,000 mPa.s at 23 ° C. and containing 0.073% Vi by weight) - POS A-2: Patterned hydrogenated oil POS Me2SiO and MeHSiO viscosity
25 mPa.s and containing 0.7% H by weight) - Surfactant (D) = either Rhodiasurf ROX 85% aqueous solution of an ethoxylated fatty alcohol marketed by Rhodia, or APV = 10% aqueous solution. polyvinyl alcohol 25/140 (4% solution viscosity: 23 / ester number: 140) of RHODOVIOL brand - Promoter (B) of adhesion and surfactant (D) = APV - Catalyst (C) = Karstedt platinum diluted in a vinylated POS oil, and titrating 10% of Pt - Resin (E.1) = 40% solution of MDV @ Q resin in a PDMS oil, # dimethylvinylsiloxy of dynamic viscosity (#dt) = 60,000 mPa. at 23 ° C., the resin solution containing 0.7% Vi by weight) (F) = ECH: Ethynylcyclohexanol.

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Weight compositions (in g):

<Tb>
<tb> PART <SEP> PART <SEP> PART
<tb> (A <SEP> 1) <SEP> (A2) <SEP> (B)
<tb> (emulsion
<tb> catalyzing)
<tb> POS <SEP> (A-1) <SEP> - <SEP> SEP <SEP> oil <SEP> 280 <SEP> 280 <SEP> 106
<tb> (F) <SEP> = <SEP> ECH <SEP> 0.7 <SEP> 0.7 <SEP> 0 <SEP>
<tb> Resin <SEP> (E.1 <SEP>) <SEP> 280 <SEP> 280 <SEP> 0 <SEP>
<tb> Surfactant <SEP> (D) <SEP> = <SEP> Rhodasurf <SEP> ROX <SEP> 35- <SEP> -
<tb> (B) <SEP> + <SEP> (D) <SEP> = <SEP> PVA <SEP> - <SEP> 162 <SEP> 56 <SEP>
<tb> POS <SEP> (A-2) <SEP> - <SEP> hydrogenated <SEP> hydrogen <SEP> 25 <SEP> 25 <SEP> 0
<tb> Catalyst <SEP> (C) <SEP> to <SEP> 10 <SEP>% <SEP> of <SEP> Pt- <SEP> - <SEP> 0.9
<tb><SEP> Sorbic acid <SEP> 0.225 <SEP> 0.225 <SEP> 0
<tb> Bicarbonate <SEP> of <SEP> soda <SEP> to <SEP> 100 <SEP>% <SEP> - <SEP> - <SEP> 1.9
<tb> Demineralized <SEP> water <SEP> 409 <SEP> 270 <SEP> 35
<tb> Total <SEP> 1030 <SEP> 1018 <SEP> 200 <SEP>
<tb><SEP> Properties of <SEP> Final SEP Emulsions
<tb> Granulometry <SEP> mean <SEP> (m) <SEP> 0.3 <SEP> 2.9 <SEP> 2.4
<tb> measured <SEP> at <SEP> Coulter <SEP> LS130
<tb> Extract <SEP> sec <SEP> (%) <SEP> (2g <SEP> 1 <SEP> h <SEP> to <SEP> 120 <SEP> C) <SEP> 59.6 <SEP> 59 , 6 <SEP> 60.9
<tb> SiH / SiVi <SEP>(SEP> molar ratio) <SEP> of <SEP> bath <SEP> 2.07
<tb> obtained <SEP> with <SEP><SEP> mixture of <SEP> 100
<tb> parts <SEP> in <SEP> weight <SEP> emulsion <SEP> A <SEP> + <SEP> 10
<tb> parts <SEP> in <SEP> weight <SEP> of emulsion
<tb> catalyzing <SEP> B
<tb> PH <SEP> of <SEP> bath <SEP> performed <SEP> by <SEP><SEP> mixing of <SEP> between <SEP> 7 <SEP> and <SEP> 8
<tb> 100 <SEP> parts <SEP> in <SEP> weight <SEP> of emulsion <SEP> A
<tb> + <SEP> 10 <SEP> parts <SEP> emulsion <SEP> catalyzing
<tb> B
<Tb>

1.2 - Procedure for the preparation of emulsions
PART (A1):
In a laboratory IKA reactor, equipped with a scraping anchor and a base (cooled by circulation of cold water), introduction of Rhodasurf ROX, 35 g of water, and POS oil (A-1 ) in which the ECH inhibitor has been previously dispersed. After stirring for 15 minutes at 80 rpm, a concentrated oil / water emulsion having the appearance of a viscous gel is obtained.

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 The resin (E.1) is then poured with stirring (80 rpm) and for 85 min, the final temperature being close to 30 ° C. The average particle size of the emulsion is then 0.28 μm.

 Stirring is continued for 30 minutes, then the oil POS (A-2) (hydrogenated polydimethylsiloxane oil) is run for 15 minutes and 80 g of water.

 At this stage, the average particle size of the emulsion characterized by Coulter LS130 is 0.29 μm.

 Dilution of the emulsion by progressive addition of the balance of demineralized water (310 g), then sorbic acid, and the final emulsion is packaged in polyethylene bottle.

PART (A2):
In a laboratory IKA reactor, equipped with a scraping anchor and a base (cooled by circulation of cold water), introduction of the 10% aqueous solution of polyvinyl alcohol (Rhodoviol 25/140) and the sorbic acid.

 The resin (E.1) is cast with stirring for 170 min, the final temperature being close to 22 C.

 The POS oil (A-1) (ViMe2SiO blocked polydimethylsiloxane oil, with a viscosity equal to 60,000 mPa.s and containing 0.07% Vi) is then poured in which the ethynylcyclohexanol (ECH) has been predispersed for 150 min. , the final temperature reaching 17 C.

 At this stage the average particle size of the emulsion characterized by Coulter LS 130 is 5.9 m.

 An Ultra-Turrax Rotor-stator (IKA) is then added and the emulsion is sheared for 1 h 30.20 min at 16000 rpm and then 1 h 10 at 13000 rpm, initial = 22.9 final CT = 28, 6 C.

 The average grain size decreases to 3 m.

 Pouring of the POS (A-2) oil (Me2SiO2 / 2 and MeHSiO2 / 2 patterned silicone oil with a viscosity of 25 mPa.s and containing 0.7% by weight) for 20 min, T = 24.5 C.

 Dilution of the emulsion by progressive addition of demineralized water for 60 min, T = 27.3 C.

PART B:
Emulsion B is produced according to the same protocol as emulsion A2, by flowing oil POS-1621 V60000 (in which the catalyst (C) was predispersed) in the 10% aqueous solution of polyvinyl alcohol. The bicarbonate is added at the end, in the diluted emulsion.

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PARTS A + B:
The mixture of 100 parts of A1 or A2 with 10 parts of B, plus possibly the dilution water to adjust the viscosity and the concentration of the bath (to adjust the amount of silicone deposited on the fabric) is achieved during the constitution of the coating bath, before application to the fabric. The bath pH is between 7 and 8.

Example 2 Method for Applying the Emulsions of Example 1
By padding (squeezing between two rolls)
The fabric arrives vertically between the rolls where the emulsion is deposited continuously, the fabric being impregnated on both sides at the outlet of the rollers. Then the fabric goes into an oven for a minute.

 The installation operates at 10 m / min. The oven temperatures are set to 120 at the input, then to 160 C output. The pressure on the squeezing rollers is of the order of 1.5 bars.

 Fabrics are weighed before and after coating to measure the weight deposited.

Example 3 Application Process of the Emulsions of Example 1
This example is identical to Example 2, with the difference that the pressure on the squeezing rolls is of the order of 1 bar.

 Fabrics are weighed before and after coating to measure the weight deposited.

EXAMPLE 4 Method for Applying the Emulsions of Example 1 By Padding (Squeezing Between Two Rolls)
The fabric is immersed in a tray placed upstream of the squeezing rollers and arrives at an angle of 20 between the rollers whose squeezing pressure is 1.5 bar., Then the fabric goes into an oven for one minute.

 The installation operates at 10 m / min. The oven temperatures are set to 120 at the input, then to 160 C output. Fabrics are weighed before and after coating to measure the weight deposited.

 Example 5: Validation in application - properties obtained with the mixture of emulsions A2 + B (without additive)

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5. 1 fabric glass weight 350g / m2
This fabric is coated according to the method of Example 4 with an emulsion according to Example 1 (mixture of emulsions A2 + B (without additive)).

The solids content of this bath was adjusted to 55.7% and then to 48%.

 Under these conditions, 22 g / m 2, expressed in sec, was deposited.

 The coated fabric has a beautiful appearance.

 The higher heating value measured according to NFP92-510 is 1900 KJ / kg.

 The resistance to fraying is good, it is materialized by a combing resistance measured according to DIN54301 greater than 35 N.

5. 2 Glass fabric weight 200 g / m2
This fabric is coated according to the method of Example 2 with an emulsion according to Example 1 (mixture of emulsions A2 + B (without additive)).

The solids content of this bath was adjusted to 55.7% and then to 42%.

Under these conditions, 15 g / m 2, expressed in sec, were deposited.

 The coated fabric has a beautiful appearance.

 The higher heating value measured according to NFP92-510 is 2150 KJ / kg.

 The resistance to fraying is good, it is materialized by a combing resistance measured according to DIN54301 greater than 35 N.

5. 3 glass fabric weight 200 g / m2
This fabric is coated according to the method of Example 3 with an emulsion according to Example 1 (mixture of emulsions A2 + B (without additive)).

The solids content of this bath was adjusted to 55.7% and then to 42%.

Under these conditions, 12 g / m 2, expressed in dry matter, was deposited.

 The coated fabric has a beautiful appearance especially on the upper face having received the emulsion.

 The higher heating value measured according to NFP92-510 is 1800 KJ / kg.

 The resistance to fraying is good, it is materialized by a combing resistance measured according to DIN54301 greater than 35 N.

 EXAMPLE 6 Incorporation into Emulsion A of Salified Amino Silane or APV During the Preparation of the Coating Bath

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Adhesion promoter addition assays have been performed to make the emulsions more adherent to glass fiber or synthetic fibers. The water-soluble silanes tested are:
6. 1 Comparative test:
The promoter is dynasylan HS 2926 sold by the company Degussa-Sivento, epoxy silane, pH = 3, 60% in water

6. 2 Test 6.2
Dynasylan HS 2929 sold by the company Degussa Sivento, amino silane and condensed and salified acrylic, pH = 4, 60% in water

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6. 3 Test 6.3
The promoter is Silquest VS 142 sold by Witco-OSI, amino silane, pH = 12, at approx. 25% in water, which consists of a silane oligomer described below, partially condensed via its SiOH.

 This silane was used after preliminary salification obtained by neutralization of the aqueous solution by addition of a quantity of acetic acid sufficient to reduce its pH to between 6 and 7.

 These promoters of the tests 6. 1, 6. 2, 6. 3 are added directly to the portion A2 of the emulsion of Example 1, 24 H before the bath (mixture A2 + B) is carried out at a rate of 2 % (by weight of dry silane relative to the oil). As soon as the bath is made, screen-printing and peeling fabric coating tests are carried out with the protocol described in the appendix. The polyester and cloth-like glass cloth adhesion results, expressed by the peel force (measured in N / (g / m 2), according to a 180 peel test described below) are shown in FIGS. and 2 appended.

 Figure 1 corresponds to a polyester fabric textile.

 Figure 2 corresponds to a fabric made of glass fabric.

Note: in the 2 figures, the control corresponds to the adhesion results obtained when the fabric is treated with the emulsion prepared as described in ≈1.2 of Example 1, without adding additional adhesion promoter.

 It is noted that the amino and salified silanes significantly improve the adhesion to glass fabric. The amino and saline silane 6. 2 also improves the adhesion to polyester fabric.

<Desc / Clms Page number 32>

The 180-coat test on fibrous support is a measure of the adhesion of PA emulsions. The procedure of this test is as follows:
1. Principle
Measurement of the force required to detach 2 strips of media coated with the test mixture and crosslinked on architectural textiles.

2. Reagents
Use of Methylene blue to facilitate the identification of the superposition of the 2 coated fabric strips (not essential to the measurement).

 3. Equipment - 1 heating press: set the temperature of the trays at 120 C.

 - 2 ovens: one at 80 C and one at 160 C - installation for application by silk screen mode (use of a wire mesh diameter - 200 m).

 - 1 Balance - 1 Dynamometer LHOMARGY DY 30.

4. Procedure a- Preparation of specimens * Support fabric used:
Cutting strips of -12 by 17 cm in the architectural textile.

To facilitate this cutting and to avoid fraying, the contours traced on the fabric are coated with a rapidly cold-curing silicone elastomer (CAF). So using a gun is deposited small amounts of CAF that is spread with a spatula along the contours. Once the CAF is dry, cutting will be easier.

* Preparation of the mixture:
10 g of Part B for 100 g of Part A. It takes -20 g of mixture to prepare 3 tests. 1 drop of methylene blue is added to facilitate the superposition of the 2 coated faces.

<Desc / Clms Page number 33>

b- Application
By silkscreen mode, 2 strips of 10 cm by 5 of the mixture are deposited, in parallel and at a distance of - 2 cm. The piece of textile is weighed before and after coating to know the quantity deposited.

 * Drying and crosslinking in press: - 5min to 80 C - superposition of the 2 coated surfaces one on the other - 5 min in press at 120 C (deposit between 2 sheets of paper), at # 2 Tons - 5 min at 160 C let stand at room temperature for 1/2 day.

6. 4 Application tests with mixtures Part A1 + B, A1 + B +
VS142 salified, A1 + B + APV:
These impregnations are carried out on a glass fabric support (200 g / m 2) by padding according to Example 3. The samples are passed in an oven at 150 ° C. for 2 min. The deposited weights are comparable and representative.

The combing resistance tests are performed to determine the ability of the samples to resist fraying.

<Tb>
<Tb>

Part <SEP> Weight <SEP> Deposit <SEP> Resistance <SEP> at
<tb> combing
<tb> (DIN <SEP> 54301)
<tb> A1 <SEP> + <SEP> B <SEP> 18-20 <SEP> 11
<tb> A1 <SEP> + <SEP> B <SEP> + <SEP> VS <SEP> 142 <SEP> salified <SEP> 18 <SEP> 44
<tb> A1 <SEP> + <SEP> B <SEP> + <SEP> 1.8 <SEP>% <SEP> APV <SEP> 19 <SEP> - <SEP> 20 <SEP> 24
<tb> A1 <SEP> + <SEP> B <SEP> + <SEP> 3.6 <SEP>% <SEP> APV <SEP> 17 <SEP> 14 <SEP>
<tb> A1 <SEP> + <SEP> B <SEP> + <SEP> 5.4 <SEP>% <SEP> APV <SEP> 16 <SEP> - <SEP> 19 <SEP> 16
<Tb>

It has been observed that the best resistance to fraying materialized by the combing test is obtained thanks to the composition A1 + B + VS 142 (presence of saline amino silane)

Claims (1)

 1. A process for producing architectural silicone membranes by coating an architectural textile with at least one layer of silicone elastomer, characterized in that it comprises the following steps: # a deposition step on said architectural textile; at least one layer of an aqueous polyorganosiloxane (POS) elastomeric crosslinkable emulsion by polyaddition reactions and comprising: (A) at least one POS having per molecule at least two C2-C6 alkenyl unsaturated functional groups; , bonded to silicon, (B) at least one POS having per molecule at least three silicon-bonded hydrogen atoms (C) at least one special adhesion promoter selected from the group of compounds including protective hydrocolloids, silanes and and / or the hydroxylated POSs per molecule of at least one hydroxyl group and at least one amine and salified function, and mixtures thereof, with the condition according to which the weight percentage of the adhesion promoter (C) relative to the silicone phase is strictly in the range from 0.005 to 10%, preferably from 0.03 to 5% and more preferably from 0.05 to 4%, (D) at least one catalyst, (E) at minus one surfactant, (F) optionally at least one POS resin comprising at least two alkenyl groups, (G) at least one crosslinking inhibitor, (H) optionally at least one pH-fixing agent, (I) optionally at least one additive of formulation, (J) optionally a filler, (K) and water, # then a crosslinking step, so as to obtain an architectural textile coated with an elastomer layer, so that the ratio of the weight of the coating expressed in dry matter to the weight of the architectural textile is less than 0.2 and preferably between 0.05 and 0.11. <Desc / Clms Page number 35>  -2- Method according to claim 1, characterized in that the deposition step is a coating step.  -3- Method according to claim 2, characterized in that the coating is performed by squeegee, in particular by squeegee on cylinder, scrapes in the air and scrapes on carpet, padding, in particular by squeezing between two rollers or by squeegee roll, rotary frame, reverse roll, transfer, screen printing, heliography, or spraying.  Process according to any one of Claims 1 to 3, characterized in that the architectural textile comprises fibers and / or yarns chosen from the group of materials comprising: glass, silica, metals, ceramics, silicon carbide, carbon, boron, natural fibers such as cotton, wool, hemp, flax, artificial fibers such as viscose, or cellulosic fibers, synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofibers, polyolefins, synthetic rubbers, polyvinyl alcohol, aramids, fluorofibres, phenolics.  -5- A method according to any one of claims 1 to 4, characterized in that the architectural textile when selected from inorganic materials has, once coated, a higher calorific value (PCS) less than or equal to 4200 KJ / Kg.  -6- architectural silicone membrane obtained from an architectural textile: - by deposition on the latter of at least one layer of an aqueous emulsion of polyorganosiloxane (POS) crosslinkable elastomer by polyaddition reactions, and adapted to the impregnation of architectural textiles, and comprising: (A) at least one POS having per molecule at least two silicon-bonded C2-C6 alkenyl unsaturated functional groups, (B) at least one POS having per molecule at least three silicon-bonded hydrogen atoms (C) at least one special adhesion promoter selected from the group of compounds comprising protective hydrocolloids, silanes and / or hydroxylated POSs <Desc / Clms Page number 36>  molecule of at least one hydroxyl group and at least one amino and salified function, and mixtures thereof, with the condition that the weight percentage of the adhesion promoter (C) relative to the silicone phase is strictly in the range from 0.005 to 10%, preferably from 0.03 to 5% and more preferably from 0.05 to 4%, (D) at least one catalyst, (E) at least one surfactant, (F) optionally at least one POS resin comprising at least two alkenyl groups, (G) optionally at least one crosslinking inhibitor, (H) optionally at least one pH-fixing agent, (I) optionally at least one formulation additive, ) optionally a charge, (K) and water, then by crosslinking the POS contained in the emulsion deposited on the textile.  Membrane according to claim 6, characterized in that it consists of a textile comprising fibers and / or yarns chosen from the group of materials comprising: glass, silica, metals, ceramics, carbide silicon, carbon, boron, natural fibers such as cotton, wool, hemp, flax, artificial fibers such as viscose, or cellulosic fibers, synthetic fibers such as polyesters, polyamides, polyacrylics, chlorofibers, polyolefins, synthetic rubbers, polyvinyl alcohol, aramids, fluorofibres, phenolics.  -8- Membrane according to claim 6 or 7, characterized in that its higher heating value (PCS) is less than or equal to 4200 kJ / kg and preferably less than or equal to 2500 kJ / kg.  -9- Membrane according to one of claims 6 to 8 or obtained by the method according to one of claims 1 to 5, characterized in that it is intended for indoor and outdoor architecture or sun protection.  Membrane according to Claim 9, characterized in that it has a weight of less than 1200 g / m2 and preferably of between 100 and 500 g / m2.